Aromatic hydrocarbon conversion process



Nov. 19, 1963 c. E. HEMMINGER AROMATIC HYDROCARBON CONVERSION PROCESS Filed July '7, 1960 Inventor/ Charles E. Hemminger By /yn M v Patent Attorney United States 3,111,546 Anorvrarrc t-rrnnocamson cons/'naaien encens-s The present invention relates to the preparation of desirable aromatic hydrocarbon constituents for motor fuels and related compositions. The invention particularly concerns -a disproportionation process wherein certain alkylated aromatic hydrocarbons are converted to more desirable homologs by means of a disproportionation reaction catalyzed by hydrogen fluoride land boron iiuoride.

One process that has been widely used for improving the quality of petroleum fractions, particularly in the medium and heavy naphtha boiling ranges, is that known as catalytic reforming or hydroforming. Hydroforming is defined as an operation in which a petroleum naphtha is contacted at elevated temperatures and pressures in the presence of added hydrogen and a suitable catalyst under such conditions that there is no net consumption of hydrogen. The hydroforming process causes dehydrogenation of naphthenes to the corresponding aromatics, isomen'zation of naphthenes, and some reactions involving any parafdns that may be present. The latter reactions may include isomeiization, aromatization and hydrocracking. rThe overall result is that the octane rating of the naphtha is increased. However, certain of the components of a powerfonnate are inferior to others in their antiknock performance; More specifically, it has been noted that the leaded Research Octane Number of orthoxylene is in in the order of 85-89 as compared to 11G-115 for the other xylenes. For aviation gasoline or for premium automotive fuel, it is desirable to increase the octane rating of the orthoxylene by converting it to other materials. rf'his can be accomplished by a disproportionation reaction.

`.lt is one object of the present invention to provide an improved process `for disproportionating the xyiene components of an aromatic hydrocarbon fraction. ln accordance with the invention, a highly aromatic hydrocarbon fraction which, for example, may be a powerformate or a selected cut thereof, is contacted with boron fluoride and hydrogen fluoride `to form a complex which is then fed into a fracitonating tower. A temperature gradient is maintained in the tower so that lighter hydrocarbons may be yremoved overhead and thereby shift the equilibrium in the complex so as to favor the production of lighter aromatics rather than the xylenes, while at the same time reducing the concentration of ortho to paraxylenes. It is a particular feature of the process f'tnat the hydrogen lluoride and boron iluoride which are also carried overhead are recovered and recycled to the bottom of the fractionating tower to aid the reaction by extending the life of the complex in the tower and by serving to strip light hydrocarbons from the complex.

In preparing the complex, a molar excess of boron uoride Ias related to the aromatic hydrocarbons is provided and, in addition, a mol ratio of hydrogen fluoride to boron fluoride of from about 2:1 to about 6:1 is present. 'I'he complexing is carried out in a temperature range of 120 to 200 F., and preferably at about 130 F. The contact time necessary to form the aromatic complex which is soluble in the liquid HF-EP3 solution depends on the degree of mixing and character of the feed. It is usually in the range of 5 to 30 minutes.

The disproportionation reaction also produces a heavy aromatics bottoms product which is in the form of a complex with BF3 `and HF. it is another feature of the presarent ent invention that this complex after removal from the tower is decomposed and the recovered BF3 and are returned to the system, i.e., either to the complexing zone or to the fractionation tower or both.

The nature of the invention and the manner in which the process can be conducted Will be better understood when reference is made to the accompanying drawing in which the single -FlGURE represents a schematic flow plan of Vthe process.

Referring now to the figure, a suitable highly aromatic feed, which may, for example, be a dried reformate of high octane rating, is introduced by means of line 11 into a preliminary fractionator 12 where benzene and toluene as well as most of the paraiins that boil below the xylenes are removed overhead by means of line i3. The resulting heavier fraction, which will contain xylenes, ethylbenzene, and C3 and heavier aromatics, is conducted by means of lines i4 and 22 to a complexing zone 24. The latter zone comprises a vessel having suitable mixing equipment. Required proportions of BF3 and HF are conducted into this zone by means of line 25, and conditions are maintained to form the complex in the liquid phase.

As an alternative to the concentration of the aromatics for complexing, a suitable solvent extraction technique could be employed. Still another alternative is represented in 4the figure. In this alternative, the feed is sen-t by means of line l5 into a preliminary treating zone 16 wherein the feed is contacted with HF at atmospheric tempera-tures -and with suificient pressure to supply about 20-30 weight percent of liquid FF. As much as 2 to 10 percent by weight of BF3 may also be added. These materials may be conducted into zone 16 by means of line i7. This treatrnent causes the formation of a complex with the aromatics while the paraiiins do not enter into the complex. The mixture of paraihns :and complex is conducted by means of line 18 into a settling zone 20 wherein the paraiiins may be separated from the complex as an upper layer and removed by means of line 2l.. The separated complex is then conducted by means of line 22 into complexing zone 24. Additional HF and BF3 are then added to the complex to provide the molar excess of BF3 in the proportion of HF to BF3 mentioned above.

The complex formed in zone 24 is conducted by means of line 26 into a mid portion of a distillation column 2S. A temperature gradient is maintm'ned in tower 23 by means `of a suitable reflux 31 at the top ofthe tower and a reboiler 32 -at the bottom ofthe tower. Sufcient holding time is provided in zone 24 and/or in distillation tower 28 to bring about the desired disproportionation. This causes the ortho and paraxylenes to be converted to metaxylene, and at the same time ethylbenzene and isopropylbenzene are disproportionated to benzene and Ito higher boiling aromatics.

The benzene and converted xylenes are remo-ved `along with HF and BF3 overhead from the tower and conducted by means of line 30 to separation zone 35. In the latter zone, the EP3 and HF are remo-ved overhead by means of line 36 and returned by means of lline 37 to the bottom of distillation tower ZS. This recycle stream of BF3 and HF acts as a mixing medium to agitate the liquid in the tower and also serves to strip lighter hydrocarbons from the complex in the tower. At the same time, the HF and EP3 serve to replace `the complexing agent that is carried overhead lfrom the rtower and thus aid in the disproportionation reaction. liecycled BF3 and HF may also be diverted to complexing zone 24 by means of line 35.

Suitable temperature and pressure conditions are maintained in the tower so that the desired light aromatic fraction will be removed overhead. These conditions will depend somewhat upon the composition of the feed,

the amount of HF and BFS recycled, `and other variables but, in general, the pressures will range somewhere between 300 and 700 p.s.i.g. A representative temperature gradient in :the tower will range from 150 F. at the top and 200 F. at the bottom.

The desired product of the reaction will be removed from separation zone 35 by means of line 39 As previously mentioned, this product will be higher in benzene content and in metaxylene content than the feed. The benzene and rnetaxylene are suitable raw materials for chemical purposes as well as more desirable components for ymotor fuels. For example, the benzene constitutes a high octane number, high volatility blending component where gasoline speciiications call for a 50% boiling point less than 212 F. Also, the conversion of orthoxylene to the higher octane rating metaxylene is advantageous, as previously mentioned.

The bottoms from tower 2S comprise a complex of highly alkylated aromatics with BFS and HF. These are removed by means of line 33 and may be conducted to a stripping zone 42 through pressure reduction valve 41 which is operated `at a relatively low temperature and reduced pressure to prevent tar formation during decomposition of the complex. `Representative conditions are temperatures in the range of 75 to 125 l?. and pressures of to 50 p.s.i.a. The BFg and HF taken overhead in line 43 are compressed to the operating pressure of tower 28 by means of compressor 45, returned to the tower by means of line 46, and injected at suitable points in the tower by means of lines `46a and 46h. The B113 and HF in line 46 may also be conducted to complexing zone 24 by means of line 48.

The heavy aromatics obtained in zone 42 are removed by means of line 50. These may then be water-washed, subjected to bauxite treatment, and given any further desirable treatment to remove residual acidic material, and may then be used in diesel fuels as a high specific gravity blending component or may be added to heavy fuel oils to serve as fluxing agents.

The aromatic concentrate stream in line 14 will contain about 10 percent paraiins and about 2 percent naphthenes when the feed in line 11 is a 99 octane number powerformate. These paratlins are cracked and disproportionated as the aromatics 4are disproportionated in the system including zone y214 and tower 28. The light hydrocarbons will pass overhead in line 3% from fractionator 28 and can 'be removed as a side stream S1 in fraotionator 35. Light gases such as methane and ethane will go overhead from tower 35 along with the BF3 and HF gases. To avoid dilution of the latter gases a purge stream is withdrawn through line 36. The BFS-HF in the purge `stream is recovered by known conventional means (not shown) such as absorption or adsorption. The higher paraiiinic hydrocarbons which are formed are associated with the heavy aromatics and are removed from the system through line 50.

When the feed in line il is rich in paraiiins in the 250 F. plus Vfraction as when, for example, a lower octane reformate .is fed, it is advantageous to feed butanes, preferably isobutane, .through lines S2 and 37 to fractionator 23. Thus, a concentration of butanes in the order of 15 to 35% is built up in the 'EP3-HF recycle stream in line 3'7. The presence of the isobutane in fractionator 121-8 directs the paraffin disproportionation reaction so that isobutane is consumed and most of the resulting parainic product is recovered from fractionator-reactor Z through 4line 33 and from the system through line 50.

The following is a representative example of the conversion of a powerformate fraction employing this invention.

Example 100 volumes of a powerformate having a Research Octane Number, unleaded, of 99 are fed into fractiona- ,urnas ai. tor i2. The powerformate has the following composition:

Volumes O-xylene 6.5 M-xylene 12.1 P-xylene 4.5 Ethyl benzene 9.7 09+ aromatics 9.4

Separation in tower 12 is such as to carry the 250 F. final boiling fraction overhead. The overhead fraction has the following composition.

Volumes Parafns 30.9

Benzene 4.1

Toluene 22.8

The bottoms from fractionator 12 are complexed in zone 24 with 1.5 liquid volumes of BF3 Iand 10 liquid volumes of HF. The complex is fed to tower `Z which is maintained at a pressure of 500 p.s.i.g. and has a top` temperature of 150 F. and a bottom temperature of 200 C9 aromatics 10 volumes of C10-C16 aromatics are obtained in line 50.

It will be understood that this invention is not to be limited to the specific embodiments and examples herein presented, as modiiications thereof Within the spirit and scope of the invention are contemplated. The invention is defined -by the claims appended hereto.

What is claimed is:

1. The process of converting a highly aromatic hydrocarbon fraction, said fraction including mixed xylenes, which comprises contacting said fraction with boron fluoride and hydrogen iluoride in a complexing zone for a time sumcient to form a complex with substantially all of said mixed xylenes, there being present a molar excess of boron iluoride as related to aromatic hydrocarbons and a mole ratio of hydrogen fluoride to boron fluoride of from about 2 to 1 to about 6 to 1, said complexing being carried out at a temperature in the range from about to 200 F., transferring said complex to a fractionation zone, disproportionating the aromatic components of said complex mixture, said fractionation zone being maintained at a pressure in the range of from about 300 to 700' p.s.i.g., and having a temperature gradient which increases from a temperature of about F. at the top of said zone to a temperature of about 200 F. at the bottom thereof wherein under said conditions a liquid-vapor state is maintained in said fractionation zone, removing from said fractionation zone an overhead :gaseous stream containing HF, BPB and a light aromatic fraction, separating said HF and BPB from said overhead stream, continuously recycling said separated HF and BFS into the bottom portion of said fractionation zone which contains liquid, and removing from said bottom of said fractionation zone a complex of heavy aromatics, EP3 and HF 2. Process as defined by claim 1 including the steps of decomposing ythe said complex of heavy aromatics, BF3, and HF and returning the thereby separated BFS and HF to at least one of the zones comprising the complexing zone and the fractionation zone.

3. Process as dened `by claim 1 wherein said highly aromatic fraction comprises the 250 F. plus fraction of the product obtained in ythe hydroforming of a petroleum naphtha.

4. Process as dened by claim 1 wherein the said aromatic fraction contains paranic hydrocarbons, and including the steps of subjecting the said fraction to a preliminary contacting with HF whereby a complex with aromatics is formed, thereafter separating paran hydrocarbons from the last-named complex, and thereafter conducting `the separated complex to said complexing zone.

5. Process as deined by claim 1 wherein the said aromatic fraction contains paran hydrocarbons, and inciuding the step of injecting a butane into said fractionation Zone.

References Cited in the file of this patent UNITED STATES PATENTS Brooke et al Sept. 5, 1950 Lien et a1 Aug. 14, 1951 McCaulay et a1. June 30, 1953 Shoemaker Dec. 13, 1955 McCauley et a1 Oct. 9, 195 6 Thorne etal Dec. 11, 1956 McOaulay et a1 Feb. 5, 1957 Fragen Aug. 19, 1958 

1. THE PROCESS OF CONVERTING A HIGHLY AROMATIC HYDROCARBON FRACTION, SAID FRACTION INCLUDING MIXED XYLENES, WHICH COMPRISES CONTACTING SAID FRACTION WITH BORON FLUORIDE AND HYDROGEN FLUORIDE IN A COMPLEXING ZONE FOR A TIME SUFFICIENT TO FORM A COMPLEX WITH SUBSTANTIALLY ALL OF SAID MIXED XYLENES, THERE BEING PRESENT A MOLAR EXCESS OF BORON FLUORIDE AS RELATED TO AROMATIC HYDROCARBONS AND A MOLE RATIO OF HYDROGEN FLUORIDE TO BORON FLUORIDE OF FROM ABOUT 2 TO 1 TO ABOUT 6 TO 1, SAID COMPLEXING BEING CARRIED OUT AT A TEMPERATURE IN THE RANGE FROM ABOUT 120 TO 200*F., TRANSFERRING SAID COMPLEX TO A FRACTIONATION ZONE, DISPROPORTIONATING THE AROMATIC COMPONENTS OF SAID COMPLEX MIXTURE, SAID FRACTIONATION ZONE BEING MAINTAINED AT A PRESSURE IN THE RANGE OF FROM ABOUT 300 TO 700 P.S.I.G., AND HAVING A TEMPERATURE GRADIENT WHICH INCREASES FROM A TEMPERATURE OF ABOUT 150*F. AT THE TOP OF SAID ZONE TO A TEMPERATURE OF ABOUT 200*F. AT THE BOTTOM THEREOF WHEREIN UNDER SAID CONDITIONS A LIQUID-VAPOR STATE IS MAINTAINED IN SAID FRACTIONATION ZONE, REMOVING FROM SAID FRACTIONATION ZONE AN OVERHEAD GASEOUS STREAM CONTAINING HF, BF3 AND A LIGHT AROMATIC FRACTION, SEPARATING SAID HF AND BF3 FROM SAID OVERHEAD STREAM, CONTINUOUSLY RE- 